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The highly regiospecific synthesis and crystal structure determination of 1,1 '-2,5 ' substituted ring-locked ferrocenes

Lookup NU author(s): Lucinda Male, Emeritus Professor Bill Clegg, Dr Luca Russo

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Abstract

1,1'-Ferrocene biscarboxaldehyde (1) has been prepared and the aldehyde groups were subsequently protected with acetal groups to produce 1,1'-bisacetalferrocene (2). A ring-locked ferrocene was synthesised by further derivatisation of the cyclopentadiene rings at the 2,2' positions with phosphine substituents to produce 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene (3), which was subsequently coordinated to either a nickel chloride (5) or nickel bromide (6) metal centre. The ring-locked ferrocene complexes produced 2,5'-bis-(acetal)-1,1'-diphenylphosphinoferrocene substitution patterns. The acetal protecting groups of 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene were removed to produce 1,1'-bis-carboxaldehyde-2,2'-diphenylphosphinoferrocene (4). The Cp rings of 1,1'-bisacetalferrocene were also further derivatised at the 2,2' positions with a silane to produce the ring-locked 1,1'-siloxane-2,5'-bisacetalferrocenophane (7). The acetal protecting groups were removed from this to produce 1,1'-siloxane-2,5'- ferrocenophanecarboxaldehyde (8). For both the phosphine and siloxane electrophiles, the substitution on the Cp rings gives chiral products (obtained as racemic mixtures). Due to the highly regioselective nature of the reaction and diastereoselectivity in the products only C-2-symmetric compounds were observed without the presence of meso diastereoisomers. Subsequent ring-locking forced the Cp rings to rotate, leading to 1,1'-ring-locked ferrocenes with 2,5'-arrangement of the acetal groups (i.e. on opposite faces of the ferrocene unit). (c) 2009 Elsevier B.V. All rights reserved.


Publication metadata

Author(s): Connell A, Holliman PJ, Butler IR, Male L, Coles SJ, Horton PN, Hursthouse MB, Clegg W, Russo L

Publication type: Article

Publication status: Published

Journal: Journal of Organometallic Chemistry

Year: 2009

Volume: 694

Issue: 13

Pages: 2020-2028

ISSN (print): 0022-328X

ISSN (electronic): 1872-8561

Publisher: Elsevier S.A.

URL: http://dx.doi.org/10.1016/j.jorganchem.2009.01.049

DOI: 10.1016/j.jorganchem.2009.01.049


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